摘要
针对2-甲氧亚胺基乙酰乙酸乙酯卤化反应中成本高、收率低、反应时间长、产品质量不稳定等问题,采用氯气为卤化试剂,对2-甲氧亚胺基乙酰乙酸乙酯氯化反应进行了相关的实验研究和机理分析。主要考察了该氯化反应的反应热、温度和酸性条件对顺反异构体的影响,同时采用多级溢流釜和动态管式反应器以实验的方式实现了该氯化反应的连续化反应工艺,并进行了连续化实验探索。由结果可知,涉及的烃化物氯化反应放热量为161.387 4 kJ/mol,优化反应温度10—20℃,酸性反应条件利于反式异构体转化为目标产物,实验结果和机理分析一致。溢流釜式连续化制备的目标产物高于现实生产中的90%,反式副产物低于现实生产中的7%,充分说明了该生产工艺可以实现连续化合成工艺。
Aiming at the problems of high cost,low yield,long reaction time and unstable product quality in the halogenation reaction of ethyl 2-methoxyimine acetoacetate,relevant experimental research,and mechanism analysis of the chlorination reaction of ethyl 2-methoxyimine acetoacetate was studied.The reaction heat of chlorination was mainly measured,and the effects on cis-trans isomerization selectivity under different temperature and acidity were mainly investigated.Meanwhile,a multi-stage overflow kettle and a dynamic tubular reactor were used to realize the continuous reaction process of the chlorination reaction in an experimental way,and the continuous experimental exploration was carried out.The results provide that the reaction heat release of the chlorination of hydrocarbons involved is 161.3874 kJ/mol,the optimal reaction temperature is 10-20℃,and the acidic reaction conditions are conducive to the conversion of trans isomers into target products,which are consistent with the mechanism analysis.The target product of overflow kettle continuous preparation is higher than 90%in actual production,and the trans by-product is lower than 7%,which fully demonstrates that the production process can realize continuous synthesis process.
作者
孟宪强
崔希礼
胡瑞华
穆海波
廉宏艳
张俊梅
任侠
MENG Xian-qiang;CUI Xi-li;HU Rui-hua;MU Hai-bo;LIAN Hong-yan;ZHANG Jun-mei;REN Xia(Shandong Jincheng Pharmaceutical Research Institute Co.,Ltd.,Zibo 255300,Shandong Province,China;Shandong Jincheng Pharmaceutical&Chemical Co.,Ltd.,Zibo 255100,Shandong Province,China;Northwest Electric Power Design Institute Co.,Ltd.,Xi′an 710075,Shaanxi Province,China;College of Chemical Engineering,Qingdao University of Science&Technology,Qingdao 266000,Shandong Province,China)
出处
《化学工程》
CAS
CSCD
北大核心
2023年第5期89-94,共6页
Chemical Engineering(China)
基金
山东省自然科学基金资助项目(ZR2020MB122)
山东省科技攻关重点项目(2019GSF109009)。
关键词
2-甲氧亚胺基乙酰乙酸乙酯
氯化反应
顺反异构
连续化制备
ethyl 2-methoxyimine acetoacetate
chlorination reaction
cis-trans isomerization
continuous preparing process
